Resinous phenol-aldehyde derivatives



United States Patent ce 2,705,704

Patented Apr. 5, 1955 1 A further object is to provide a process for preparing such resinous compositions. 2 7 704 A still further object is to provide coating compositions containing said resinous compositions and articles coated RESINOUS PHENOL-ALDEHYDE DERIVATIVES 5 merewlth- Ben Edmund Sorenson, Drexel Hill, Pa., assignor to E. I. as the description of the invention proceeds, are accomdu Pont de Nemours and Compan Wilmington, DeL, plished by reacting (1) an adduct of a preformed phenola corporation of Delaware aldehyde resin and a compound containing the oxirane o No Drawing. Application October 3, 1952, m Serial No. 313,043 im- 7 Claims. (Cl. 260-51) g group with (2) material selected from the class c onsist-.

product of said aldehyde and said alcohol. This invention relates to new resinuous compositions The adducts arebelieved to have a structure in accordderived from adducts of preformed phenolaldehyde resins time With the following slmphfied emP1P!cal formula! In a, R [R a J R R and compounds containing the oxirane in which R, R, 'R1 and R2 are the same as previously defined. They are prepared by reactmg an oxirane comphenol-aldehyde resin as disclosed in the literature, e. g. U. S. Patents 2,060,410; 2,076,624; 2,454,541 and I I 2,598,234. b h l The oxirane com ound ma e an of t e ar e rou group. More specifically it relates to resins wh ch are of compounds contgining y g g p the reaction products of such adducts and aliphatic aldehydes together with aliphatic monohydric alcohols.

It is an object of this invention to provide resinous 2 compositions having an empirical structure exemplified l by the following formula: CyChC oxide radical, for Instance, ethylene oxide, 1,2

R1 R1 O(CHr( JHO)..R|OR; 0(CHzH0hRaOR: ()(CHzHOhRzORr t R a R R a La R J R in which: propylene oxide, 1,2 butylene oxide, styrene oxide, vinyl R and R aremonovalent radicals selected from the cyclohexene oxide, allyl glycidyl ether, phenyl glycidyl group consisting of the hydrogen, alkyl, alkenyl, alicyclic, ether and epiethylin (ethyl glycidyl ether). aryl and alkaryl radicals; v The phenol-aldehyde resin may be the condensation R is a monovalent radical selected from the group product of a large variety of phenols and aliphatic aldeconsisting of the hydrogen, methyl, ethyl, phenyl, hydes which are well own in the phenolic resin art.

-CH2O alkyl, -CH2O alkenyl and CH2O aryl radi- Examples of suitable phenols are phenol; alkyl subcals. Thus stituted phenols such as cyclohexyl phenol; alkenyl subp stituted phenols such as butenyl phenol; aryl substituted (CHIHO) Y phenols such as phenyl phenol; and alkaryl substituted henols such as di hen 101 ro ane. Mixtures of such represents the divalent residue of n mols of a compound 51 1 may b gl gz p p which originally contained the While formaldehyde or paraformaldehyde is usually 0 employed as the aldehyde 1n the phenol-aldehyde condensation product, other aliphatic aldehydes may be used 1 1 such as acetaldehyde and butyraldehyde. (oxirane group). In preparing the phenol-aldehyde resin, the ingredients R2 is a divaleht radical Selected f the group are usually reacted 1n the presence of an acidic or alkaline Sign-Hg of the CH2 CHQCH, CHsCHzCH-and catalyst until the product has become viscous to solid v CHaCHzCHZCH when cooled to room temperature. The adduct of the phenol-aldehyde condensate and radicals and represents the residue'of an aliphatic C1-C4 h xirane compound is usually prepared by dissolving yde. The R2 radlcals Wh Ch f Im t brldges and reacting the ingredients at an elevated temperature tween the Phenolic uhlts y h the Same as of different in a closed vessel in the presence of a catalyst. An inert than the R2 in the RzORs radlcal; solvent such as toluene may be included.

a is a monovalell} alkyl fadlQal n represfcnts the The invention involves reacting the above described adresidhe Of an aliphatlc monohydllc alcohol; duct with an aliphatic aldehyde and an aliphatic monois a number equal to greater than 1 and hydric alcohol or with an acetal-type condensation prod- I is an integer equal to greater than not of said aldehyde and said alcohol, whereby all or part It is to be unders ood at the of the hydroxyl hydrogen atoms in the formula for the R1 adduct are replaced by the R2OR3 group, in which R2 (-CHKEHO) is ahelregidlue of said aldehyde and R3 is the residue of sat a co 0 dwalent group may also be wntten as A simple example of such a reaction is the treatment of an adduct, resulting from the reaction of a preformed l A 1 (t JHCmO) phenol-formaldehyde resin and ethylene oxide, with paraformaldehyde and n-butyl alcohol. In this case the R2OR3 substituent group is "-"CH2OC4H9. Other a1de= hydes such as formaldehyde, acetaldehyde or butyraldeyde may be empl a v a o e alc l u h as methyl. ethyl, propyl, amyl or octyl.

Another example is the treatment of the same adduct with formal, CH2(OCI- Is )z,' which is an acetal-type condensation productof formaldehyde and methyl alcohol. In this case the -RgOR substituent group is The following specific examples illustrate this invention but are not intended as a'lirnitation 'thereof. Unless otherwise specified, the parts are by weight.

Example 1 Parts, Adduct =279 n-Butyl alcohol- Toluene s'olvent- Toluene sulfon ic ac d catalyst; Paraformaldehyde;; 30 1 The adduct was a phenolic resin prepared by the acid condensation of 7 mols of phenol and 6 mols of formaldehydeand modified with 21 mols of propylene o a ide (1. e. 3 mols per phenolichydroxyl group); A convenient abbreviated descr1p tion is phenol:formaldehydemropylene oxide-426cm. The adduct, alcohol, toluene and catalyst were placed in a vessel equipped with an ag tator,"'a thermometer with the bulb, below -the liquid level and..a reflux condenser havlng a water, separator. I to about 85 C. and agitated until a uniform solution formed, i. e. about minutes. Theuparaformaldehyde The charge washeated mmp 4 Reaction temperature: 85-12 O C. R and R'=hydro'gn.

. R and R'=hydrogen.

Example 5 Adduct (phenol:formaldehydezethylene oxide- 7:6:10.5) Isobutyl alcoholn Toluene solvent Toluene sulfonic acid catalyst--- was added and the mixture was refluxed. During a Paraformaldehydfi 49 period of about 2% hours, water wasrempved from the. condensate and the temperature was gradually increased Rcactlon temperature=8S -ll2-C. to about 120 C. The reaction was considered com- R and R'=hyd g plete when no further water separated out. of the distilf Y Q- late. The acid catalyst was neutralized by refluxing with R2=CH2. calcium carbonate, and the charge was filtered. R3=C4Ha. The product was a relatively viscous solution of a resin n=l.5. having the following empirical formula:

O(CsHsO)3 H2OC 4H9 O(CaHsO)aCHzOC Ha"\ O(CaHeO)sCHaOC4Ha CH CH L 1. It will be seen that the above compound has the formula V Example hew ni e ee ntl Par g a h fi s 9 nW n 1 Parts R @313 re re s R1 1 R? 13 R? 151041-719; Adduct (phenol'formaldehydeistyrene .oxide-.- VHS 3 and'x 1S 1. .931 270 xamp which lo mploy e, me p- """"'7"';'"" 120 pe Pr cedur as xamr e h e: w q Toluene Solvent 120 monotonous repetition; thereactants, temperatures sub Toluene i"; ;f 2'**"'- 3 stituent radicals, etc., are merely tabulated. Paraformaldeh'yd 30 Example, 2 Reaction temperature=-l2 2 C. P R and R'=hydrogen.

- arts 60 R1==CsH5-. Adduct. (phenol:formaldehyde.:propylene oxide R 7:6:7.7) .J: :"531 Z n-Butyl alcohol 380 33 Toluene solvent 240 Toluene sulfonic acid catalyst 4 5 T Paraformaldehyde, p 7

- I Parts Ractlofl P Adduct (phenolzformaldehyde:allylzglycidyl:-ether- R and y e 7:6:8.75)' H 49,4 7 n-Butyl alcohol -Q 218 Toluene solven I 4 g 250 Toluene sulfonicfacid catalyst, V, l 4 2 Paraformaldehyde,L;.,. f..; i 30.

' Reaction temperature=85+l26 C.

Erample 3 75 R'and R'-=hydr.ogen.

' Parts R1=CH2OCH2CH=CH2.

- R2=CH2. Adduct (phenol:formaldehydezpropylene oxrde- R H 7:6:35) 396 3 n-Butyl alcohol ":5 sulfuric acid 50% formaldehyde (aqueous') Examnlefi Reaction temperature-:BS-J'JS" C. i Parts- R and R'.= hydrogen. Adduct (phenol:formaldehydezphenyl glycidyl K; -;C I-I 35 ether7:6:7.7) ..l' 217 Isobutyl alcohol 168 Toluene solve 96 Toluene sulfonic acid catalyst 0.8 Paraformaldehyde 38.0

Reaction temperature=85-l3 1 C. R and R=hydrogen. RI=CH2OC6H5- Parts Adduct (phenol:formaldehydezpropylene oxide- 7:6:l0.5) 192 Formal CH2(OCH3)2 228 Toluene sulfonic acid catalyst 3 Reaction temperature=40-45 C.

R and R=hydrogen.

Methyl alcohol was the byproduct of the reaction rather than water as in previous examples. When the reaction was complete, 192 parts of toluene were added and the temperature was raised to about 115 C. to distill off the unreacted formal, yielding a toluene solution of the resin.

Ethyl alcohol was the by-product of the reaction rather than water as in Examples 1-8.

Example 11 Parts Adduct (paratertiary butyl phenolzformaldehyde:

ethylene oxide--:9:12) 214 n-Butyl alcohol Toluene sulfonic acid catalyst 1 Paraformaldehyde 36 Reaction temperature=85133 C. R=hydrogen. R'=(CH3)3C. R1=hydrogen. R2=CH2. R3==C4H9. n=1.2. 36:3.

Example 12 Parts cresol:formaldehyde:propylene Adduct (ortho oxide-10:10:12) n-Butyl alcohol Toluene solvent Toluene sulfonic acid catalyst Paraformaldehyde Reaction temperature=85-127 C. R=hydrogen. R=CH3. R1=CH3. =CHz. =C1H9. =11.

x=approximately 15 compared with tion).

While the examples employ a wide variety of ingredrents, it is obvious that only a small proportion of the possible combinations Within the scope of this invention has been illustrated. For instance, other phenol-aldehyde resins, oxirane compounds, alcohols and aldehydes, which have been previously disclosed, may be used. Furthermore, the invention is not limited to employing single members of these groups in a given product, since mixtures of two or more members may be used when desirable. Also other acid catalysts, such as benzene disulfonic acid, phosphoric acid and hydrochloric acid, and other solvents, such as xylene, naphtha, mineral spirits, ethers, esters, alcohols, or mixtures thereof, may be used.

The resinous products of this invention are particularly useful as coating compositions when used alone, in admixture with other film-forming materials, such as urea formaldehyde resins, melamine formaldehyde resins, oil modified alkyd resins, and natural gums, or in admixture with finely divided pigments such as titanium dioxide, iron oxides, iron blues, lead or zinc chromates and organic pigments. The coating compositions may be applied by any conventional method such as dipping, brushing or spraying.

The following examples illustrate such uses:

Example 13 The product of Example 1 was applied to a steel panel by dipping, and the coated panel was baked for 30 minutes at 400 F. The coating was hard, glossy, and insoluble in toluene. The panel was exposed outdoors for several months during which the coating protected the metal from rusting.

Panels coated similarly with the products of Examples 2-l2 showed that these products also protected steel from rusting.

In general, the neutralized products of this invention require relatively high baking temperatures to convert them to the insoluble (cured) state. However, if a bakingcatalyst is incorporated in the composition prior to application, low baking temperatures may be employed, such as -150 R, which make these products use ful for coating wooden furniture and the like. The baking catalyst may be, for instance, octyl acid phos phate, benzene sulfonic acid or, if so desired, residual acid catalyst purposely retained in the product by not neutralizing or only partially neutralizing the catalyst present during preparation.

Example 14 butyl alcohol IGSID.

A pigmented enamel having the above formula was prepared by grinding the ingredients in conventional paint grinding apparatus until the pigment Was finely divided and uniformly dispersed in the mixed resin solu- .tions.

The resulting enamel was thinned with toluene to a suitable consistency and was sprayed on an aluminum panel which was baked for 30 minutes at 300 F. The coating was hard, glossy and relatively flexible and compared favoraby in simulated service tests with a conventional coating containing titanium dioxide, ureaformaldehyde resin and oil-modified alkyd resin.

Coating compositions may also be made from resinous materials prepared by heating a product of Examples l-l2 with another resinous film-forming material, preferably under reflux distillation conditions, instead of by merely mixing the cold solutions.

The preferred products of this invention are those in which substantially all of the hydroxyl hydrogen atoms of the adduct are replaced by the RzORa radical; however, useful products may be prepared by replacing only a portion of said hydrogen atoms.

Although any aliphatic C1-C4 aldehyde may be used in the practice of this invention to produce useful resins,

it is preferred to use formaldehyde or paraforrnaldehyde spirit and scope thereof and, therefore, it is not intended for economic reasons. Also, for economic reasons, the to be limited except as indicated inv the appended claims.

preferred phenols are phenol, tertiary butyl phenol and I claim: cresol, the preferred oxirane compounds are ethylene l. Aresinous composrtionhaving the empirical formula Iir If! r R1 C(CHzCHOhRzORs O(CHZC'HO)7|R2OR3 C(CHzJJIIOMRzORg R1 -R2 R i if! LR R l B R oxide and propylene oxide, and the preferred monoin which: hydric alcohols are methyl, ethyl, propyl and butyl R and R are monovalent radicals selected from the alcohol. 15 group consisting of the hydrogen, cyclohexyl, alkyl, al-

The empirical formula for the products of this invenkenyl, aryl and alkaryl radicals; tion, which is shown in the second paragraph of this Rr is a monovalent radical selected from the group specification, discloses an average of l or more mols of consisting of the hydrogen, methyl, ethyl, phenyl, --CHzO oxide per phenolic hydroxyl group, i. e. 11:1 or greater. alkyl, C 2 allienyl and CH2 aryl a al The preferred range is 1-5 because values greater than 0 R2 1s a divalent ra .Sfi from the group about 5 represent products having an undesirable sensitivmg of the CH2 CHsCH, CHaCHaCI-I and CHsCH-zCHzCH .ity to water. radicals and represents the residue "of an aliphatic CrC4 The empirical formula also discloses 1 or more recuryf rent structural units within the brackets; i. e. x=1 or R3 15 a monovalent alkyl Yadlcal and mpfe-senis greater. The preferred range is 1-15 because values 25 residue of an aliphatic monohydri alcohol? mber equal to at least 1 and greater than about 15 represent products having such a a x 18 an integer equal to at least 1.

hi h molecular weight that they are insoluble or drfficultly 2 The product of claim 1 in which n is L5.

soluble in ordinary solvents,'or solutions thereof are more 3 The product of claim 1 in which x is 1 15 5Com than can be handled conveniently 9 I 4. A coating composition comprising the product of The products of this invention are useful as coating claim compositions for both fiexible and rigid surfaces, adhesives, 5 A coating composition comprising the product of molding compounds, emulsifiers, plasticizers, laminating claim 1 and another resinous fil f i materiaL materials and as intermediates for further chemical proc- 6 A oating composition comprising the product of essing. 5 claim 1 and finely divided pigment.

It is apparent that many widely different embodiments 7. An article coated with a composition comprising of this invention may be made without departing from the the product of claim 1.

References Cited in the file of this patent FOREIGN PATENTS 434,903 Italy May 4, 1943" 443,195 Italy Dec. 10, 1948 

1. A RESINOUS COMPOSITION HAVING THE EMPIRICAL FORMULA 